Magnetism in Double Perovskites

Double-perovskite compounds with general formula ABB′O₆, have attracted a lot of attention in recent years due to a variety of properties exhibited by them. In this paper, we will review our recent study on a number of double-perovskite compounds, namely La-doped Sr₂FeMoO₆, Cr-based family of compounds, Sr₂CrXO₆ (X=W, Re, Os), characterized with spectacularly high ferromagnetic transition temperatures and the magneto-capacitive compound, La₂NiMnO₆, We will discuss the signature of hybridization-driven antiferromagnetism in La-doped Sr₂FeMoO₆, while the parent compound, Sr₂FeMoO₆, is a half-metallic ferromagnet. The magnetism in the 3d–5d double perovskite Sr₂CrXO₆ (X=W, Re, Os) is found to be driven by the interplay of the hybridization-driven mechanism and the superexchange, which resulted into progressive increase of T _c as one moves from W to Re to Os at the B′ site. Our work, in the context of La₂NiMnO₆, identifies its superexchange-driven microscopic origin being responsible for the near room-temperature insulating ferromagnetic behavior.     

Halide Perovskites for Nonlinear Optics

Halide perovskites provide an ideal platform for engineering highly promising semiconductor materials for a wide range of applications in optoelectronic devices, such as photovoltaics, light-emitting diodes, photodetectors, and lasers. More recently, increasing research efforts have been directed toward the nonlinear optical properties of halide perovskites because of their unique chemical and electronic properties, which are of crucial importance for advancing their applications in next-generation photonic devices. Here, the current state of the art in the field of nonlinear optics (NLO) in halide perovskite materials is reviewed. Halide perovskites are categorized into hybrid organic/inorganic and pure inorganic ones, and their second-, third-, and higher-order NLO properties are summarized. The performance of halide perovskite materials in NLO devices such as upconversion lasers and ultrafast laser modulators is analyzed. Several potential perspectives and research directions of these promising materials for nonlinear optics are presented.     

3D Nanoprinting of Perovskites

As competing with the established silicon technology, organic–inorganic metal halide perovskites are continually gaining ground in optoelectronics due to their excellent material properties and low‐cost production. The ability to have control over their shape, as well as composition and crystallinity, is indispensable for practical materialization. Many sophisticated nanofabrication methods have been devised to shape perovskites; however, they are still limited to in‐plane, low‐aspect‐ratio, and simple forms. This is in stark contrast with the demands of modern optoelectronics with freeform circuitry and high integration density. Here, a nanoprecision 3D printing is developed for organic–inorganic metal halide perovskites. The method is based on guiding evaporation‐induced perovskite crystallization in mid‐air using a femtoliter ink meniscus formed on a nanopipette, resulting in freestanding 3D perovskite nanostructures with a preferred crystal orientation. Stretching the ink meniscus with a pulling process enables on‐demand control of the nanostructure's diameter and hollowness, leading to an unprecedented tubular‐solid transition. With varying the pulling direction, a layer‐by‐layer stacking of perovskite nanostructures is successfully demonstrated with programmed shapes and positions, a primary step for additive manufacturing. It is expected that the method has the potential to create freeform perovskite nanostructures for customized optoelectronics.     

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

Despite the exciting progress on power conversion efficiencies, the commercialization of the emerging lead (Pb) halide perovskite solar cell technology still faces significant challenges, one of which is the inclusion of toxic Pb. Searching for Pb‐free perovskite solar cell absorbers is currently an attractive research direction. The approaches used for and the consequences of Pb replacement are reviewed herein. Reviews on the theoretical understanding of the electronic, optical, and defect properties of Pb and Pb‐free halide perovskites and perovskite derivatives are provided, as well as the experimental results available in the literature. The theoretical understanding explains well why Pb halide perovskites exhibit superior photovoltaic properties, but Pb‐free perovskites and perovskite derivatives do not.     

Defect Activity in Lead Halide Perovskites

The presence of various types of chemical interactions in metal‐halide perovskite semiconductors gives them a characteristic “soft” fluctuating structure, prone to a wide set of defects. Understanding of the nature of defects and their photochemistry is summarized, which leverages the cooperative action of density functional theory investigations and accurate experimental design. This knowledge is used to describe how defect activity determines the macroscopic properties of the material and related devices. Finally, a discussion of the open questions provides a path towards achieving an educated prediction of device operation, necessary to engineer reliable devices.     

Multiple-Quantum-Well Perovskites for High-Performance Light-Emitting Diodes

Light-emitting diodes (LEDs) based on solution-processed metal halide perovskites have shown great application potential in energy-efficient lighting and displays. Multiple-quantum-well (MQW) perovskites simultaneously possess high photoluminescence quantum efficiency and good film morphology and stability, making it attractive for high-performance perovskite LEDs. Here, merits of MQW perovskites and the progress in MQW perovskite LEDs are reviewed. Challenges and future directions of perovskite LEDs are also discussed.     

A-Site Management for Highly Crystalline Perovskites

An in-depth understanding and effective suppression of nonradiative recombination pathways in perovskites are crucial to their crystallization process, in which supersaturation discrepancies at different time scales between CH₃NH₃I (MAI, methylammonium iodide) and PbI₂ remain a key issue. Here, an A-site management strategy via the introduction of an A-site placeholder cation, NH₄⁺, to offset the deficient MA⁺ precipitation by occupying the cavity of Pb–I framework, is proposed. The temporarily remaining NH₄⁺ is substituted by subsequently precipitated MA⁺. The temperature-dependent crystallization process with the generation and consumption of a transient phase is sufficiently demonstrated by the dynamic changes in crystal structure characteristic peaks through in situ grazing-incidence X-ray diffraction and the surface potential difference evolution through temperature-dependent Kelvin probe force microscopy. A highly crystalline perovskite is consequently acquired, indicated by the enlarged grain size, lowered nonradiative defect density, prolonged carrier lifetime, and fluorescence lifetime imaging. Most importantly, it is identified that the A-site I_MA defect is responsible for such crystal quality optimization based on theoretical calculations, transient absorption, and deep-level transient spectroscopy. Furthermore, the universality of the proposed A-site management strategy is demonstrated with other mixed-cation perovskite systems, indicating that this methodology successfully provides guidance for synthesis route design of highly crystalline perovskites.     

Controlled Homoepitaxial Growth of Hybrid Perovskites

Organic–inorganic hybrid perovskites have demonstrated tremendous potential for the next‐generation electronic and optoelectronic devices due to their remarkable carrier dynamics. Current studies are focusing on polycrystals, since controlled growth of device compatible single crystals is extremely challenging. Here, the first chemical epitaxial growth of single crystal CH₃NH₃PbBr₃ with controlled locations, morphologies, and orientations, using combined strategies of advanced microfabrication, homoepitaxy, and low temperature solution method is reported. The growth is found to follow a layer‐by‐layer model. A light emitting diode array, with each CH₃NH₃PbBr₃ crystal as a single pixel, with enhanced quantum efficiencies than its polycrystalline counterparts is demonstrated.     

Coated and Printed Perovskites for Photovoltaic Applications

Hybrid organic–inorganic metal halide perovskite semiconductors provide opportunities and challenges for the fabrication of low‐cost thin‐film photovoltaic devices. The opportunities are clear: the power conversion efficiency (PCE) of small‐area perovskite photovoltaics has surpassed many established thin‐film technologies. However, the large‐scale solution‐based deposition of perovskite layers introduces challenges. To form perovskite layers, precursor solutions are coated or printed and these must then be crystallized into the perovskite structure. The nucleation and crystal growth must be controlled during film formation and subsequent treatments in order to obtain high‐quality, pin‐hole‐free films over large areas. A great deal of understanding regarding material engineering during the perovskite film formation process has been gained through spin‐coating studies. Based on this, significant progress has been made on transferring material engineering strategies to processes capable of scale‐up, such as blade coating, spray coating, inkjet printing, screen printing, relief printing, and gravure printing. Here, an overview is provided of the strategies that led to devices deposited by these scalable techniques with PCEs as high as 21%. Finally, the opportunities to fully close the shrinking gap to record spin‐coated solar cells and to scale these efficiencies to large areas are highlighted.     

Inorganic and Layered Perovskites for Optoelectronic Devices

Organic–inorganic halide perovskites are making breakthroughs in a range of optoelectronic devices. Reports of >23% certified power conversion efficiency in photovoltaic devices, external quantum efficiency >21% in light‐emitting diodes (LEDs), continuous‐wave lasing and ultralow lasing thresholds in optically pumped lasers, and detectivity in photodetectors on a par with commercial GaAs rivals are being witnessed, making them the fastest ever emerging material technology. Still, questions on their toxicity and long‐term stability raise concerns toward their market entry. The intrinsic instability in these materials arises due to the organic cation, typically the volatile methylamine (MA), which contributes to hysteresis in the current–voltage characteristics and ion migration. Alternative inorganic substitutes to MA, such as cesium, and large organic cations that lead to a layered structure, enhance structural as well as device operational stability. These perovskites also provide a high exciton binding energy that is a prerequisite to enhance radiative emission yield in LEDs. The incorporation of inorganic and layered perovskites, in the form of polycrystalline films or as single‐crystalline nanostructure morphologies, is now leading to the demonstration of stable devices with excellent performance parameters. Herein, key developments made in various optoelectronic devices using these perovskites are summarized and an outlook toward stable yet efficient devices is presented.